O-ethyl-s-m-propyl-o-(2,6-dichloro-4-bromophenyl)phosphorothiolate

ABSTRACT

New phosphoric acid ester of the formula   and its use for combating insects and members of the order acarina are disclosed.

United States Patent [191 Drabek O-ETHYL-S-M-PROPYL-O-(2,6-DICl-ILORO- 4-BROMOPHENYL)PHOSPHOROTHIO- LATE [75] Inventor: Jozef Drabek, Allschwil, Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: Dec. 20, 1973 [21] App1.No.: 426,777

[30] Foreign Application Priority Data Dec. 22, 1972 Switzerland [8732/72 [52] US. Cl 260/964; 424/225 [51] Int. Cl. A01n 9/36; CO7f 9/18 [58] Field of Search 260/964 [56] References Cited UNITED STATES PATENTS 3,663,665 5/1972 Kume et a1. 260/964 X 3,839,511 10/1974 Kishino et a1. 260/964 FOREIGN PATENTS OR APPLICATIONS 2,163,391 7/1972 Germany 260/964 51 July 22, 1975 500,230 12/1970 Switzerland ..260/964 [57] ABSTRACT New phosphoric acid ester of the formula and its use for combating insects and members of the order acarina are disclosed.

1 Claim, N0 Drawings 1 2 O-ETHYL-S-M-PROPYL-O-(2,6-DICHLORO-4- c I BROMOPHENYL )PHOSPHOROTHIOLATE czHso 3 m P O B r (n)C H S The present invention relates to the thiolphosphoric c 1 acid ester of th f r u a to processes for the preparation thereof, and to its application in pest control.

The compound of formula I can be prepared by the 10 following processes:

0 d b d C H O [I aci in ing 13) 2 5 P-CI+ o Br (n)C H1 u agent can n it) 1+ M. Br------ 1 c1 Iv) c no u 2) 2 PCI+ H0 l l l I o C2I-I5O ll acid binding PO Br +HSC H,(n)- 1 CI vll gent I (VI) Cl MeSC I-I (n)-- C 1 (Vin 5 3a) C H O u CzHso B I (R):1N

M Cl (IX) (X) C l )2$e S I 0 1| C2I-I5NC PO +(n)C,,H-,Hal

X1!) (X1) CI C I I s s c n o 1| 3b) c H o B ROC-SMe (n)C I-I HaI c (x11 (IX) or MeSR (XIV) or Mc S (XV) or MeSI-I (XVI) 3 -Continued 1 ll Cl acid binding 4 c,n,,o-P H Cl agent (XVIII) I S I '1 O MeS f" B +MeoH- P- 2 Cl xx) c I (XXI) (XIX) In the formulae IV, VII, VIII, X, XI, XIII, XIV, XV, XVI, XVI] and XX, Me stands for an alkali metal, especially for sodium or potassium, ammonium or alkylammonium; R stands for C C -alkyl such as methyl'or ethyl; and Hal for chlorine, bromine or iodine.- 1

Suitable acid binding agents are: tertiary amines, e.g. trialkylamines, pyridine, dialkylanilines; inorganic bases such as hydrides or hydroxides; carbonates and bicarbonates of alkali metals and alkaline-earth metals. Sometimes it is necessary in the reactions to use catalysts such as, e.g. copper or copper chloride. The processes .la and lb, 2, 3 and 3b and 4 are performed at a reaction temperature of between 0 and 130C, under normal pressure and in solvents or'diluents inert to the reactants.

Inert solvents or diluents which are suitable are, e.g. ethers and ethereal compounds such as diethyl ether, dipropyl ether, dioxane or tetrahydrofuran; amides such as N,N-dialkylated carboxylic acid amides; aliphatic, aromatic as well as halogenated hydrocarbons, particularly benzene, toluene, xylenes', chloroform qr chlorobenzene; nitriles such as acetonitrile; or dimethylsulphoride. Also alcohols and water are suitable in the case of processes 3a and 3b.

The starting materials of formula II can be produced by methods analogous to known methods, e.g. by those described in J. orig. Chem. 30,3217 (1965).

Compared with analogous compounds from the Swiss Patent Specification No. 500,230 and from the German Offenlegungsschrift No. 2,163,391, the compound of formula I has a surprisingly better insecticidal and acaricidal action, particularly against Heliothis virescens larvae and Chilo suppressalis larvae, and a toxicity suitable for application. The action of the compounds according to the invention extends, in addition, to all development stages, such as, e.g. eggs, larvae, nymphs, pupae and adults of insects .of the families: Acrididae. Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, -'Aphididae, Delpha cidae, Diaspididae, Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae,

Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae, Tipulidae, Stomoxydae, Muscidae,

. Calliphoridae, Trypetidae, Pulicidae, as well as acarids of the families: lxodidae, Argasidae, Tetranychidae, Dermanyssidae.

The insecticidal or acaricidal action can be appreciably broadened and adapted to suit the given circumstances by the addition of other insecticides and/or acaricides. Suitable additives are, for example:

organic phosphorus compounds, nitrophenols and derivatives, formamidines,

carbamates and chlorinated hydrocarbons.

The agents according to the invention are prepared in a known manner by the intimate mixing and/or grinding of the active substance of formula I with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances. The active substances can be obtained and used in the following forms:

solid preparations: dusts, scattering agents, granulates,

coated granulates, impregnated granulates, and homogeneous granulates, liquid preparations:

a. water-dispersible active-substance concentrates:

wettable powders, pastes or emulsions; b. solutions.

Dusts a) 10 parts of active substance,

The following substances are used in the preparation 3'4 pans of epoxidised Vega-able on Of a) a 5% dust, and b) a 2% 'CluStZ 13.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt, 5 40 parts of dimethylformamide, a) 5 parts of active substance, 43.2 parts of xylene.

95 parts of talcum;

b) 25 parts of active substance, b) 2 parts of active substance, 2.5 parts of epoxidised vegetable oil,

1 part of highly dispersed silicic acid, 10 parts of an alkylarylsulphonate/fatty alcohol- 97 parts of talc m, polyglycol ether mixture l0 5 parts of dimethylformamide,

. parts of xylene.

57.5 The active substancesare mixed and ground Wlth the From these concentrates it is possible to produce, by

carriers.

dilution with water, emulsions of .any desired concen- Granulate 1 5 tuition The following substances are used to produce a 5% granulate: spray The following constituents are used to prepare a 5% s ra 5 parts of active substance, p y 0.25 parts of epichlorhydrin,

0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 5 P8115 0f aq 91 parts of kaolin (particle size 0.3 0.8 mm). 1 part of epichlorhydrm.

' 94 parts of ligroin (boiling'limits 160-190C).

The active substance is mixed with epichlorhydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed on to'kaolin, and the acetone subsequently evaporated off in vacuo.

EXAMPLE 1 Preparation of the compound of theformula C l O Wettable powder C H O H 2 The following constituents are used for the prepara- 5 Br tion of a) a 40%, b) and c) a 25%, and d) a 10% wetta' (")CQHTS ble powder: C l

i i 40 f v b An amount of 35.2 g of 2,6-dich1oro-4-bromophenol a parts 0 aCtlV SL1 stance,

5 parts of Sodium lignin Sulphonate 1S d ssolved in 150 ml ofbenzene, and 15.1 of triethyl 1 part of sodium dibutylnaphthalene amine then added. While continuous stirring IS mam- 54 sultzlstotz ati d tained, an addition is made dropwi'se at 1015C of v 3.1 0 S1 ICIC 3C1 b) 3 of active substance, 40 32.0 g of O-ethyl-S-(n) propylchlorothtophosphate. 4.5 parts of calcium lignin sulphonate Stirring 1s afterwards continued for -12 hours at room Pans of chalk/hydmxyeflyl temperature. The mixture is subsequently washed with cellulose mixture (1:1), 1.5 parts of sodium dibutyl naphthalene water, 5% Na CO -solut1on, and again with water, it IS 19 5 sul horgattla, d then dried over anhydrous sodium sulphate. The benparts 0 S1 lClC 3C1 195 parts. of Champagne Chalk. zeneis dist illed off and the residue .PUUFCCI by molecu 23,1 pans f ka n, lar distillation (bOllll'lg temperature 150 C/0.001 Torr). 5 P a g- 1 th 1 The ester of the above given formula is obtained hav- 53: y p enoxy'po yoxye yene' ing a refractive index of n 1.5576. 1.7 parts of Champagnechalk/hydroxyethyl Analysis: for C11 H14 B1 Cl 03 P S cellulose mixture (1:1), 50 8.3 parts of sodium aluminum silicate. 16.5 parts of kieselguhr I 46 pans of kaolin Calculated. Found. d) 10 parts of active substance, 1

3 parts of a mixture of the sodium salts of Z g saturated fatty alcohol sulphates, 0 r 5 parts of naphthalenesulphonic a'cid/formal- 55 dehyde condensate, 82 parts of kaolin.

EXAMPLE 2 w The act ve substance is intimately mixed, in suitable comparative Tests m1xers, with the additives, and the mixture then ground Active Substances in the appropriate mills and rollers. Wettable powders t are obtained which can be diluted with water to give suspensions of any desired concentration. O c 1 A C I-1 O ll Emulsifiable concentrates I H B r The following substances are used to produce a) a 1 15 according) the c invention 10% and b) a 25% emulsifiable concentrate:

known from DOS 2.163.391

1 known from DOS 2,163,391. and from SP. 500,230"

Tests Insects Heliotlris virescens larvae.

Chilo suppressalis larvae,

Aedes aegypti larvae,

Ripicep/zalus bursa (adults and larvae).

Test emulsion 10 parts of active substance.

3.4 parts of epoxidised vegetable oil. 3.4 parts of a combination emulsifier consisting of tetraalcohol polyglycol ether and alkylarylsulphonate calcium salt. 40 parts of dimethylformamide, 43.2 parts of xylene.

Test granulate 5 parts of active substance. 0.25 parts of epichlorohydrin, 025 parts of ethyl po'lyglycol ether. 3.5 parts of polyethylene glycol. 91.0 parts of kaolin (particle size 0.3 to 0.8 mm).

TOT (idly Result LD rat 9': destroyed after 8 days with 500 ppm orally (mg/kg) of active substance C 20%- I50- I b. Action Against Chilo'Suppressalis Rice plants of the variety Caloro were planted, 6 plants per pot, in plastic pots having a. top diameter of 17 cm, and grown to a height of ca. 60 cm. Infestation with Chilo suppressalis larvae (L 34 mm long) was carried out 2 days after application of the active substance in granular form (amount applied 8 kg of active substance per hectare) to the paddy water. The assessment of the insecticidal action was made 10 days after application of the granulate.

Result destroyed after 10 days with 400 ppm A l00% B 0% 0. Action Against Ticks Rhipicephalus bursa I In each case, 5 adult ticks or 50 tick larvae were placed into a small glass test tube, and the test tubes then immersed for l to 2 minutes in 2 ml of an aqueous emulsion from a dilution series of 100, l0, 1 and 0.1 ppm of test substance. The tubes were then sealed with a standardised cotton plug, and inverted so that the active substance emulsion could be absorbed by the cotton wool. I

An evaluation was made in the case of the adults after 2 weeks, and in the case of the larvae after 2 days. There were two repeats for each test.

Result Active substance action with X pm against Rliipicepha us bursa Adults Larvae A 0.1 0.1 B 5 0.1 C 'l l d. Action Against Mosquito Larvae (Aedes Aegypti) An amount of 1 ml of an aceton solution of the test substances was transferred by pipet into 100 ml of water in a beaker, so that the concentration was 1 ppm or 0.1 ppm.-

Eight days after the treatment, 4-day-old Aedes aegypti larvae were applied and the destruction of the insects estimated in per cent.

While compound A in Tests a) to d) has an almost 100% action against Heliothis virescens and Chilio suppressalis larvae, adults and larvae of Rhipicephalus bursa and mosquito larvae, compounds B and C are insufficiently effective or ineffective in the tested concentrations. I

What we claim is:

1. Compound of the formula 

1. COMPOUND OF THE FORMULA O-P(=O)(-O-C2H5)-O-C3H7 